EP2657317B1 - Matériau luminescent d'oxyde de gallium-indium et son procédé de préparation - Google Patents

Matériau luminescent d'oxyde de gallium-indium et son procédé de préparation Download PDF

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Publication number
EP2657317B1
EP2657317B1 EP10861149.2A EP10861149A EP2657317B1 EP 2657317 B1 EP2657317 B1 EP 2657317B1 EP 10861149 A EP10861149 A EP 10861149A EP 2657317 B1 EP2657317 B1 EP 2657317B1
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Prior art keywords
luminescent material
indium oxide
gallium indium
solution
gaino
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German (de)
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EP2657317A1 (fr
EP2657317A4 (fr
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Mingjie Zhou
Jun Liu
Wenbo Ma
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Oceans King Lighting Science and Technology Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/87—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing platina group metals
    • C09K11/873—Chalcogenides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
    • C09K11/621—Chalcogenides

Definitions

  • the present invention relates to the field of luminescent materials, and in particular relates to a gallium indium oxide luminescent material doped with metal nanoparticles.
  • the present invention also relates to a method for preparing a gallium indium oxide luminescent material.
  • sulfide systems such as blue powders ZnS:Ag,Cl and SrGa 2 S 4 :Ce, green powder SrGa 2 S 4 :Eu, and red powder Y 2 O 2 S:Eu
  • oxide systems such as blue powder Y 2 SiO 5 :Ce, green powders ZnGa 2 O 4 :Mn, Y 2 SiO 5 :Tb and Y 3 Al 5 O 12 :Tb, and red powder Y 2 O 3 :Eu.
  • oxide series has relatively poor stabilities.
  • the oxide series has lower electrical conductivities than the sulfide series.
  • the surface of the luminescent material may be coated with a conductive material, such as In 2 O 3 , SnO 2 , ZnO, etc., and luminescent materials having certain electrical conductivities are studied.
  • the present invention provides a gallium indium oxide luminescent material doped with metal nanoparticles, which has high electrical conductivity and good chemical stability.
  • the gallium indium oxide luminescent material has a chemical formula of: GaInO 3 :zM; wherein M represents a metal nanoparticle which may be one or two selected from the group consisting of Ag, Au, Pt and Pd, and z may be in the range of 1 ⁇ 10 -5 ⁇ z ⁇ 0.02.
  • Another object of the present invention is to provide a method for preparing the above gallium indium oxide luminescent material, which comprises the steps of:
  • the source compound of In and the source compound of Ga may be corresponding nitrates thereof, respectively.
  • the chelating agent may be citric acid monohydrate, and the molar ratio of the chelating agent to the overall metal ions (Ga ions and In ions, i.e., trivalent Ga ions and trivalent In ions) in the mixed solution may be 1:1 to 5:1;
  • the crosslinking agent may be polyethylene glycol with a molecular weight of 2000-20000, and the molar ratio of the crosslinking agent to GaInO 3 may be 0 to 1:100.
  • the surface-treated M nanoparticle sol may be prepared with the steps of:
  • Step S3 of the above preparation method the process of heating in a water bath while stirring comprises: heating in a water bath at 60 to 90 °C while stirring; and the process of drying comprises: blast drying first at 60 to 80 °C, followed by oven drying at 80 to 150 °C.
  • the pre-calcinating treatment comprises: pre-calcinating at 500 °C to 900 °C for 2 to 10 h; and the calcinating treatment comprises: calcinating at 800 to 1300 °C for 1 to 8 h.
  • the present invention has the following advantages.
  • the present invention provides a gallium indium oxide luminescent material, which has a chemical formula of: GaInO 3 :zM; wherein M represents a metal nanoparticle which may be one or two selected from the group consisting of Ag, Au, Pt and Pd, and z may be in the range of 1 ⁇ 10 -5 ⁇ z ⁇ 0.02.
  • the present invention further provides a method for preparing the above luminescent material, which, as shown in Figure 1 , comprising the following steps.
  • Step A Preparation of a metal nanoparticle sol.
  • Step B Prepartion of GalnO 3 :zM
  • the innovations of the present invention lie in that metal nanoparticles are doped in the GaInO 3 luminescent material and the luminous intensity of the luminescent material is increased through the surface plasmon resonance generated at the surface of the metal particles.
  • SP surface plasmon
  • the surface plasmon (SP) is a wave propagating along the interface of the metal and the medium, and the amplitude thereof exponentially decays with the increase of the distance away from the interface.
  • SPPs surface plasmon polaritons
  • the electromagnetic field induced by SPPs can not only limit the propagating of light waves in a sub-wavelength structure, but also generate and control electromagnetic radiations in the range of from optical frequency to microwave band, so as to achieve active manipulation of the light propagation, increase the optical density of the luminescent material and enhance the spontaneous radiation rate. Moreover, by means of the coupling effect of the surface plasmon, the internal quantum efficiency of the luminescent material can be greatly improved, so that the luminous intensity of the luminescent material is increased.
  • the molecular weight of polyethylene glycol is 2000 to 20000.
  • Example 1 Preparation of GaInO 3 :2 ⁇ 10 -2 Au by sol-gel method
  • chloroauric acid (AuCl 3 ⁇ HCl ⁇ 4H 2 O) is weighed and dissolved in 16.8 mL of deionized water. After chloroauric acid is completely dissolved, 14 mg of sodium citrate and 6 mg of cetyl trimethyl ammonium bromide are weighed and dissolved in the aqueous solution of chloroauric acid under magnetic stirring.
  • the wet gel is dried overnight in a blast oven at 60 °C, and then dried completely at 110 °C, to give a precursor, which is placed in a high-temperature furnace and pre-calcinated at 500 °C for 2 h, cooled down to room temperature, ground, then placed in a high-temperature box furnace and calcinated at 800 for 8 h, naturally cooled down and taken out to give the desired luminescent material GaInO 3 :2 ⁇ 10 -2 Au.
  • Example 2 Preparation of GaInO 3 :1 ⁇ 10 -3 Ag by sol-gel method
  • the wet gel is dried overnight in a blast oven at 70 °C, and then dried completely at 120 °C, to give a precursor, which is placed in a high-temperature furnace and pre-calcinated at 800 °C for 4 h, cooled down to room temperature, ground, then placed in a high-temperature box furnace and calcinated at 1000 for 3 h, naturally cooled down and taken out to give the desired luminescent material GaInO 3 :1 ⁇ 10 -3 Ag.
  • Example 3 Preparation of GaInO 3 :1 ⁇ 10 -4 Pt by sol-gel method
  • chloroplatinic acid H 2 PtCl 6 ⁇ 6H 2 O
  • chloroplatinic acid H 2 PtCl 6 ⁇ 6H 2 O
  • 8.0 mg of sodium citrate and 12.0 mg sodium dodecyl sulfonate are weighed and dissolve in the aqueous solution of chloroplatinic acid under magnetic stirring.
  • 0.38 mg of sodium borohydride is dissolved in 5 ml of ethanol and 5 mL of deionized water to give 10 mL of an aqueous solution of sodium borohydride having a concentration of 1 ⁇ 10 -3 mol/L.
  • the wet gel is dried overnight in a blast oven at 80 °C, and then dried completely at 150 °C, to give a precursor, which is placed in a high-temperature furnace and pre-calcinated at 900 °C for 10 h, cooled down to room temperature, ground, then placed in a high-temperature box furnace and calcinated at 1200 for 2 h, naturally cooled down and taken out to give the desired luminescent material GaInO 3 :1 ⁇ 10 -4 Pt.
  • Example 4 Preparation of GaInO 3 :1 ⁇ 10 -5 Pd by sol-gel method
  • the wet gel is dried overnight in a blast oven at 80 °C, and then dried completely at 120 °C, to give a precursor, which is placed in a high-temperature furnace and pre-calcinated at 800 °C for 4 h, cooled down to room temperature, ground, then placed in a high-temperature box furnace and calcinated at 1300 for 1 h, naturally cooled down and taken out to give the desired luminescent material GaInO 3 :1 ⁇ 10 -5 Pd.
  • Example 5 Preparation of GaInO 3 :2 ⁇ 10 -5 Pt/Au by sol-gel method
  • the wet gel is dried overnight in a blast oven at 80 °C, and then dried completely at 100 °C, to give a precursor, which is placed in a high-temperature furnace and pre-calcinated at 850 °C for 5 h, cooled down to room temperature, ground, then placed in a high-temperature box furnace and calcinated at 1300 for 1 h, naturally cooled down and taken out to give the desired luminescent material GaInO3:2 ⁇ 10 -5 Pt/Au.
  • Example 6 Preparation of GaInO 3 :4 ⁇ 10 -4 Ag by sol-gel method
  • the wet gel is dried overnight in a blast oven at 75 °C, and then dried completely at 80 °C, to give a precursor, which is placed in a high-temperature furnace and pre-calcinated at 600 °C for 5 h, cooled down to room temperature, ground, then placed in a high-temperature box furnace and calcinated at 900 for 4 h, naturally cooled down and taken out to give the desired luminescent material GaInO 3 :4 ⁇ 10 -4 Ag.
  • Figure 2 shows the comparison of the luminescent spectrum of the fluorescent powder prepared in Example 6 of the present invention under a cathode-ray excitation at an acceleration voltage of 7.0 kV; wherein curve a is the emission spectrum of the luminescent material doped with metal nanoparticles, GaInO 3 :4 ⁇ 10 -4 Ag; curve b is the emission spectrum of the luminescent material GaInO 3 .
  • curve a is the emission spectrum of the luminescent material doped with metal nanoparticles, GaInO 3 :4 ⁇ 10 -4 Ag
  • curve b is the emission spectrum of the luminescent material GaInO 3 .
  • the luminous intensity of the luminescent material increases by 85%; and the integrated area thereof increases by 97%.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Luminescent Compositions (AREA)

Claims (10)

  1. Matériau luminescent d'oxyde de gallium-indium, caractérisé en ce que la formule chimique du matériau luminescent est GalnO3:zM; sachant que M représente une nanoparticule métallique sélectionnée entre un ou deux des éléments tels que Ag, Au, Pt et Pd, et z est compris dans la plage de 1 x 10-5 ≤ z ≤ 0,02.
  2. Procédé de préparation d'un matériau luminescent d'oxyde de gallium-indium, caractérisé en ce que le procédé comprend les étapes de
    étape S1, ajouter un composé source d'In et un composé source de Ga selon un rapport stoechiométrique d'éléments correspondants dans la formule chimique GalnO3 en un solvant mélangé d'eau et d'éthanol pour préparer une solution mélangée contenant des ions In et des ions Ga ;
    étape S2, ajouter un chélateur et en option un agent de réticulation dans la solution mélangée obtenue à l'étape S1 pour préparer une solution chélatant ;
    étape S3, ajouter un sol de M nanoparticules traité en surface dans la solution chélatant préparée à l'étape S2, et chauffer au bain-marie tout en brassant, puis sécher pour obtenir un précurseur ayant une formule chimique de GalnO3:zM; sachant que M représente une nanoparticule métallique sélectionnée entre un ou deux des éléments tels que l'Ag, l'Au, le Pt et le Pd, et z est compris dans la plage de 1 x 10-5 ≤ z ≤ 0,02 ; et
    étape S4, pré-calciner le précurseur obtenu à l'étape S3, refroidir, broyer puis calciner, refroidir et broyer à nouveau pour obtenir le matériau luminescent d'oxyde de gallium-indium présentant une formule chimique de GalnO3:zM.
  3. Procédé de préparation d'un matériau luminescent d'oxyde de gallium-indium selon la revendication 2, caractérisé en ce qu'à l'étape S1, le composé source d'In et le composé source de Ga sont des nitrates correspondants de celui-ci, respectivement.
  4. Procédé de préparation d'un matériau luminescent d'oxyde de gallium-indium selon la revendication 2, caractérisé en ce qu'à l'étape S2, le chélateur est du monohydrate d'acide citrique, et le rapport molaire du chélateur au l'ensemble des ions métalliques (ions Ga et ions In) dans la solution mélangée est de 1:1 à 5:1.
  5. Procédé de préparation d'un matériau luminescent d'oxyde de gallium-indium selon la revendication 2 ou 4, caractérisé en ce qu'à l'étape S2, l'agent de réticulation est du polyéthylène glycol avec un poids moléculaire de 2000-20000, et le rapport moléculaire de l'agent de réticulation au GalnO3 est de 0 à 1:100.
  6. Procédé de préparation d'un matériau luminescent d'oxyde de gallium-indium selon la revendication 2, caractérisé en ce qu'à l'étape S3, le sol de M nanoparticules qui est traité en surface est préparé avec les étapes de :
    étape S31, peser un composé source de M et le dissoudre et le diluer dans de l'eau ou un solvant mélangé d'éthanol et d'eau présentant un rapport volumique de 1:7 à 4:1 pour préparer une solution mélangée contenant des ions M avec une concentration molaire de 2.4 x 10-4 à 3 x 10-3 mol/L ;
    étape S32, ajouter séquentiellement un additif et une solution d'un réducteur à la solution mélangée obtenue à l'étape S31 et brasser pour obtenir un sol de M nanoparticules ; et
    étape S33, ajouter le sol de M nanoparticules obtenu à l'étape S32 en une solution contenant un agent de traitement de surface et brasser pour obtenir un sol de M nanoparticules traité en surface.
  7. Procédé de préparation d'un matériau luminescent d'oxyde de gallium-indium selon la revendication 6, caractérisé en ce qu'à l'étape S32
    l'additif est au moins l'un parmi le polyvinylpyrrolidone, citrate de sodium, bromure d'ammonium de triméthyle céthyle, sulfate de sodium dodécyl et sulfonate de sodium dodécyl ; la quantité de l'additif est telle que sa teneur dans le sol de M nanoparticules final est de 1,5 x 10-4 g/mL à 2,1 x 10-3 g/mL ;
    la concentration molaire de la solution du réducteur est 1 x 10-3 mol/L à 1 x 10-2 mol/L ; le réducteur dans la solution de réducteur est au moins l'un parmi l'hydrate d'hydrazine, l'acide ascorbique et le borohydrure de sodium ; le solvant dans la solution de réducteur est de l'eau ou un solvant mélangé d'eau et d'éthanol ; et le rapport molaire du réducteur aux ions M est de 1.2:1 à 4.8:1.
  8. Procédé de préparation d'un matériau luminescent d'oxyde de gallium-indium selon la revendication 6, caractérisé en ce qu'à l'étape S33, l'agent de traitement de surface est du polyvinylpyrrolidone, et l'agent de traitement de surface est ajouté dans une quantité de 0,0002 g/mL à 0,1 g/mL.
  9. Procédé de préparation d'un matériau luminescent d'oxyde de gallium-indium selon la revendication 2, caractérisé en ce qu'à l'étape S3, le procédé de chauffage au bain-marie tout en brassant comprend : le chauffage dans un bain-marie de 60 à 90°C tout en brassant, et le procédé de séchage comprend : le séchage par soufflage d'abord de 60 à 80°C suivi d'un séchage en four à 80 à 150°C.
  10. Procédé de préparation d'un matériau luminescent d'oxyde de gallium-indium selon la revendication 2, caractérisé en ce qu'à l'étape S4, le traitement de pré-calcinage comprend : le pré-calcinage à 500°C à 900°C pendant 2 à 10h ; et le traitement par calcinage comprend : le calcinage à 800 à 1300°C pendant 1 à 8h.
EP10861149.2A 2010-12-20 2010-12-20 Matériau luminescent d'oxyde de gallium-indium et son procédé de préparation Active EP2657317B1 (fr)

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US20130202909A1 (en) * 2012-02-06 2013-08-08 Lg Chem, Ltd. Method of producing metal nanoparticles
US20150275083A1 (en) * 2012-10-31 2015-10-01 Ocean's King Lighting Science & Technology Co., Ltd Silicate luminescent material and preparation method therefor
CN104059659A (zh) * 2013-03-20 2014-09-24 海洋王照明科技股份有限公司 掺杂金属纳米粒子的钆酸钙绿光发光材料及制备方法
WO2021070021A1 (fr) * 2019-10-10 2021-04-15 King Abdullah University Of Science And Technology Système ingazno (igzo) destiné à une détection de gaz à température ambiante
CN111569856B (zh) * 2020-04-03 2023-06-09 清华-伯克利深圳学院筹备办公室 In-Ga2O3复合光催化剂及其制备方法和应用

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WO2012083517A1 (fr) 2012-06-28
US20130234077A1 (en) 2013-09-12
EP2657317A1 (fr) 2013-10-30
JP2014503645A (ja) 2014-02-13
JP5688473B2 (ja) 2015-03-25
US9068118B2 (en) 2015-06-30
EP2657317A4 (fr) 2014-10-08
CN103180408A (zh) 2013-06-26
CN103180408B (zh) 2014-07-02

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